EP0659838B1 - Copolymeres d'organopolysiloxane comme macro-initiateur radicalaire - Google Patents
Copolymeres d'organopolysiloxane comme macro-initiateur radicalaire Download PDFInfo
- Publication number
- EP0659838B1 EP0659838B1 EP94117748A EP94117748A EP0659838B1 EP 0659838 B1 EP0659838 B1 EP 0659838B1 EP 94117748 A EP94117748 A EP 94117748A EP 94117748 A EP94117748 A EP 94117748A EP 0659838 B1 EP0659838 B1 EP 0659838B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- general formula
- units
- radical
- organopolysiloxanes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 63
- 239000003999 initiator Substances 0.000 title description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- -1 aliphatic alcohols Chemical class 0.000 claims description 75
- 229920000578 graft copolymer Polymers 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 9
- 150000004756 silanes Chemical class 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 6
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910020485 SiO4/2 Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 125000005375 organosiloxane group Chemical group 0.000 abstract description 3
- 101100237844 Mus musculus Mmp19 gene Proteins 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 14
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 14
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- 238000000149 argon plasma sintering Methods 0.000 description 7
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
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- 235000021317 phosphate Nutrition 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
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- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 4
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- 229920001519 homopolymer Polymers 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
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- 241001136792 Alle Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
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- 238000004821 distillation Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001558 organosilicon polymer Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- TWANXESQHWBHNY-UHFFFAOYSA-N 3-[diethoxy(propan-2-yloxy)silyl]propan-1-amine Chemical compound CCO[Si](OC(C)C)(OCC)CCCN TWANXESQHWBHNY-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- SEAPWVKYZKVDCR-UHFFFAOYSA-N 4-cyanopentanoyl chloride Chemical compound N#CC(C)CCC(Cl)=O SEAPWVKYZKVDCR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- 239000004166 Lanolin Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
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- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 229940039717 lanolin Drugs 0.000 description 2
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- 229920002521 macromolecule Polymers 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- SYXUBXTYGFJFEH-UHFFFAOYSA-N oat triterpenoid saponin Chemical compound CNC1=CC=CC=C1C(=O)OC1C(C=O)(C)CC2C3(C(O3)CC3C4(CCC5C(C)(CO)C(OC6C(C(O)C(OC7C(C(O)C(O)C(CO)O7)O)CO6)OC6C(C(O)C(O)C(CO)O6)O)CCC53C)C)C4(C)CC(O)C2(C)C1 SYXUBXTYGFJFEH-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical group C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Definitions
- the invention relates to crosslinked organopolysiloxanes containing radical-forming groups, their preparation, graft copolymers from the organopolysiloxanes according to the invention as radical macroinitiators and radical-polymerizable organic monomers and a process for the preparation of the graft copolymers.
- graft copolymers One way of producing graft copolymers is to graft a polymer which carries a functional end group capable of reaction onto another polymer.
- This process known as the "grafting onto” process, is state of the art in the production of graft copolymers from an organosilicon polymer (core) component and an organic polymer (shell) component, as described, for example, in US Pat. No. 5,223,586.
- (mono) olefinically unsaturated, radically polymerizable monomers such as vinyl monomers
- This "grafting onto” process starts an homopolymerization of the organomonomers by means of an external redox initiator system; the growing organopolymer chains bind to the (silicone) graft base.
- An obvious disadvantage of this process is that the connection of the organopolymer to the polysiloxane is not mandatory, and thus a considerable part of the organopolymer is not grafted onto the polysiloxane, but is present as an unattached homopolymer; this can be done e.g. B. by extractions on insoluble graft copolymers from organosilicon and organic polymer components, which were prepared by the "grafting onto” method, demonstrate.
- graft copolymers are formed as a result of intramolecular linkages, in particular entanglements due to multiple attachment of the organopolymer chain to the organosilicon polymer core, which can be seen from the structural characterization of such graft copolymers, e.g. B. by means of static and dynamic light scattering.
- the object was to provide organopolysiloxanes as radical macroinitiators with which graft copolymers can be prepared from crosslinked organopolysiloxanes and organopolymers which do not have the above-mentioned disadvantages of the known graft copolymers, namely a high proportion of organopolymer homopolymer and uncontrolled structure.
- the invention relates to crosslinked organopolysiloxanes containing radical-forming groups, composed of 0.2 to 50.0% by weight of units of the general formula [R a Si (O (3-a) / 2 ) -R1-X- (R1-Si (O (3-a) / 2 )) b R a ] (1), 0 to 80.0% by weight of units of the general formula [R3SiO 1/2 ] (2), 0 to 99.5% by weight of units of the general formula [R2SiO 2/2 ] (3), 0 to 99.8% by weight of units of the general formula [RSiO 3/2 ] (4) and
- the organopolysiloxanes according to the invention are insoluble in all solvents except for a small proportion. Preferably at most 2% by weight of the organopolysiloxanes can be extracted with toluene.
- unsubstituted radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4- Trimethylpentyl, nonyl, such as the n-nonyl, decyl, such as the n-decyl, dodecyl, such as the n-dodecyl, octadecyl such as the n-octa
- substituted hydrocarbon radicals as radical R are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical as well as the chlorophenyl, dichlorophenyl and trifluorotolyl radical; Mercaptoalkyl radicals, such as the 2-mercaptoethyl and 3-mercaptopropyl radical; Cyanoalkyl radicals, such as the 2-cyanoethyl and 3-cyanopropyl radicals; Aminoalkyl radicals, such as the 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl and N- (2-aminoethyl) -3-amino- (2-methyl) propyl radical; Aminoaryl radicals, such as the aminophenyl radical; Acyloxyalkyl radicals,
- the radical R is preferably unsubstituted and substituted C1 to C6 alkyl radicals and the phenyl radical, in particular the methyl, ethyl, propyl and phenyl radical, in the general formula (1) the methyl, ethyl , Propyl and phenyl radical.
- the organopolysiloxanes according to the invention are preferably spherical microgels with particle diameters of preferably 5 to 200 nm in an aqueous medium.
- the molecular weights of the organopolysiloxane radical macroinitiators according to the invention are preferably 105 to 1010, in particular 5.105 to 109 g / mol.
- R , R4 , X , a and b have the above meanings, to a moving mixture of emulsifier and water.
- the above process is an emulsion polymerization / polycondensation process.
- organosiloxanes comprising units of the general formula (12) are preferably used as organosilicon compounds composed of units of the general formula (11) R2SiO 2/2 (12), or organosiloxanes of the general formula (13) R3SiOSiR3 (13), used.
- organosilicon compounds of the general formula (10) are tetraethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane and trimethylethoxysilane.
- organosilicon compounds composed of units of the general formula (12) preferably have 3 to 8, in particular 4 or 5, units.
- a preferred example is octamethylcyclotetrasiloxane.
- organosilicon compounds of the general formula (13) is hexamethyldisiloxane.
- Aliphatically substituted benzenesulfonic acids and their salts and quaternary ammonium halides and hydroxides are preferred.
- the amount of emulsifier to be used is from 0.5 to 20% by weight, preferably from 1.0 to 10% by weight, in each case based on the total amount of organosilicon starting compounds used.
- the organosilicon starting compounds of the general formulas (9) to (13) are added in doses. All starting components are preferably mixed in the desired ratio; In order to obtain a homogeneous mixture, an additional 0.1-30% by weight, based on the starting components, of alkanol of the formula ROH is added as a solubilizer, with the alkanols methanol, ethanol and propanol being particularly preferred are.
- the starting compounds, in particular the silanes of the general formula (10) can also not be added in a mixture, but in successive doses, but this is not preferred.
- the organopolysiloxanes according to the invention can still contain small amounts of hydrocarbonoxy radicals O R 4 and / or hydroxyl groups, but this is not preferred.
- the emulsion polymerization / polycondensation is carried out at 5-95 ° C, preferably at 10-85 ° C and particularly preferably at 10-40 ° C.
- the pH of the polymerization / polycondensation mixture is 1-12, preferably 7-11.
- the alkanol released during the hydrolysis can be removed by distillation, if appropriate under reduced pressure.
- the solids content of the organopolysiloxane dispersion produced in this way should preferably be at most 25% by weight, since otherwise a high increase in viscosity makes it more difficult to process the dispersion as a graft base.
- the free radical initiator-containing silanes are almost quantitatively incorporated into the organopolysiloxane radical macroinitiators according to the invention. This can be shown by breaking the aqueous dispersions by adding salt, isolating the radical macroinitiators in substance, washing them, drying them in vacuo at room temperature and examining them by means of differential calorimetry (DSC). As is known to the person skilled in the art, the DSC allows the measurement of amounts of heat which are taken up by a sample in the isothermal mode of operation or are given off to it. In the thermolysis z. B.
- azo group-containing compounds gives the total area under the exothermic decomposition peak, normalized to the mass of the measured sample, the decomposition enthalpy in J / g and is thus directly proportional to the azo group content of the compound. If one relates the decomposition enthalpy of a silicon network containing azo groups to the decomposition enthalpy of the starting silane containing azo groups, the actual azo group content in the silicone network can be determined.
- organopolysiloxanes according to the invention are preferably used as radical macroinitiators for the graft polymerization of ethylenically unsaturated organic monomers.
- the polymer to be grafted has a reactive group which reacts with the monomer added for the grafting.
- This process is referred to as the "grafting from” process.
- the graft branches grow directly onto the graft base, so that graft copolymers with a defined structure can be built up in a targeted and controllable manner. Due to the covalent incorporation of initiators into the polymer to be grafted, which break down into radicals and can then initiate graft polymerizations, homopolymerization of the graft monomer is only possible to a very limited extent and only by transfer reactions.
- a dispersion of the organopolysiloxanes according to the invention described above is presented as radical macroinitiators. If the dispersion has not already been produced, it is optionally freed from alcohol formed in the hydrolysis of the starting silanes by distillation at preferably 20-40 ° C. and reduced pressure and, if appropriate, diluted with water. If necessary, a further 1-15% by weight, based on the amount of free radical macroinitiator, of emulsifier is added to the dispersion, which is preferred. Preferably the same emulsifier is used that was also used to prepare the radical macroinitiator dispersion. The dispersion is preferably saturated with nitrogen for 10 to 90 minutes, the pH of the dispersion should preferably be 7-9.
- Ethylenically unsaturated organic monomers are then metered in in an amount which is 5-95% by weight, preferably 20-80% by weight, based in each case on the total weight of the graft copolymer.
- Styrene and acrylic acid esters and methacrylic acid esters of aliphatic alcohols having 1 to 4 carbon atoms for example methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate, are particularly preferred. Both homopolymers and copolymers of the monomers mentioned are suitable as organic polymer fraction.
- the grafting starting from the organopolysiloxane radical macroinitiators is preferably started by increasing the temperature to 30-90 ° C., preferably 60-85 ° C. To complete the polymerization, the starting temperature is maintained for 30 minutes to 8 hours, preferably 1-2 hours. Residual amounts of unreacted organomonomer can then be removed by distillation, which is preferred.
- the graft copolymers according to the invention can be isolated from the dispersion by known processes, for example by coagulating the latices by adding salt or adding polar solvents or spray drying.
- the invention further relates to the graft copolymers obtainable by the process according to the invention.
- the graft copolymers according to the invention are spherical particles with particle diameters of preferably 10 to 250 nm in the aqueous medium.
- the molecular weights of the graft copolymers according to the invention are preferably 106 to 101 10, in particular 5.105 to 109 g / mol.
- the graft copolymers prepared by the process according to the invention have a defined structure through targeted connection of the organopolymer chains to the silicone graft base and (silicone) core (organopolymer) shell structure.
- silicone graft base and (silicone) core (organopolymer) shell structure Depending on the content of units of the general formula (1) and thus on the density of the graft on the organopolysiloxane, star-shaped to brush-shaped graft copolymer structures are formed.
- Graft copolymers which have a soft, little crosslinked silicone elastomer core and e.g. are grafted with methyl methacrylate or styrene, can easily be spray dried and processed thermoplastically.
- the graft copolymers prepared by the process according to the invention show a significantly improved binding of the organopolymer to the silicone graft base and thus a significantly lower proportion of free organopolymer homopolymer than corresponding graft copolymers which have been prepared according to the prior art by the "grafting onto” method; this can be demonstrated by extraction experiments.
- the graft copolymers according to the invention are particularly suitable for use as modified thermoplastics or for use as additives for polymer modification.
- Static and dynamic light scattering are established methods known to those skilled in the art in macromolecular chemistry and colloid chemistry for characterizing disperse particles. Static light scattering averages the scattering intensity at various angles over a sufficiently long time interval and provides information about the static properties of the macromolecules, such as the weight-average molecular weight M w , the z-mean of the square of the radius of inertia ⁇ R g 2 > z , and the second virial coefficient A2, which describes the intra- and intermolecular thermodynamic interactions of the dispersed particles with the solvent.
- the quotient of the inertia and hydrodynamic radius provides information about the particle shape, such as a hard sphere, hollow sphere or star polymer.
- the refractive index can e.g. B. a silicone core to be adjusted to the refractive index of the dispersing medium and thus the polymer shell
- a silicone core-organopolymer shell graft copolymer can be detected alone.
- Structural information such as particle form obtained via these systems in surfactant-free form in the non-aqueous dispersion medium.
- the static and dynamic light scattering was measured with a system consisting, among other things, of a Stabilite R 2060-lls Kr laser from Spectra-Physics, a goniometer Sp-86 from ALV and an ALV-3000 digital structure / correlator.
- the krypton ion laser worked with a wavelength of 647.1 nm.
- Sample preparation The aqueous silicone radical macro initiator dispersions and other silicone network dispersions were mixed with 10 ⁇ 4 molar potassium bromide solutions, the aqueous graft copolymer dispersions with deionized water diluted with a specific conductivity of 0.056 ⁇ S / cm and the samples filtered three times through Millex R -GS filters (0.22 ⁇ m pore size) from Millipore.
- the graft copolymer dispersions in dimethylformamide were filtered three times through Millex R -FGS filters (0.2 ⁇ m pore size) from Millipore.
- the measurement temperature in the light scattering experiments was 20 ° C.
- the dynamic light scattering measurements were carried out in 20 ° steps, depending on the angle from 50 ° to 130 °, in the static light scattering experiment the angle dependence of the scattered light was measured in 30 ° steps from 30 ° to 140 °.
- DSC Differential calorimetry
- Example 2 The procedure of Example 1 was repeated with the change that 9.08 g (47.2 mmol) of methylaminopropyltrimethoxysilane were used instead of 11.06 g (47.2 mmol) of methylaminopropyltriethoxysilane. 13.4 g (90% of theory) II were obtained.
- Example 3 The procedure from Example 3 was repeated with the change that instead of a mixture of 99.0 g of methyltrimethoxysilane and 1.0 g of I, a mixture of 97.0 g (0.71 mol) of methyltrimethoxysilane and 3.0 g (4.2 mmol) I from Example 1 was metered into the initial charge.
- the stable, clear, slightly opalescent dispersion obtained had a solids content of 8.7%.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 11.0 nm and a molar mass M w of 1.5.106 were determined by means of static and dynamic light scattering. Differential calorimetry (DSC) demonstrated the quantitative incorporation of I into the silicone network.
- Example 3 The procedure from Example 3 was repeated with the change that instead of a mixture of 99.0 g of methyltrimethoxysilane and 1.0 g of I, a mixture of 95.0 g (0.70 mol) of methyltrimethoxysilane and 5.0 g (7.0 mmol) I from Example 1 was metered into the initial charge.
- the stable, clear, slightly opalescent dispersion obtained had a solids content of 8.8%.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 13.3 nm and a molecular weight Mw of 2.7.106 were determined by means of static and dynamic light scattering. Differential calorimetry (DSC) demonstrated the quantitative incorporation of I into the silicone network.
- Example 3 The procedure from Example 3 was repeated with the change that instead of a mixture of 99.0 g of methyltrimethoxysilane and 1.0 g of I, a mixture of 97.0 g (0.71 mol) of methyltrimethoxysilane and 3.0 g (12.1 mmol) of methacryloxypropyltrimethoxysilane was dosed to the template.
- the resulting stable, clear, slightly opalescent dispersion had a solids content of 8.5%.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 9.3 nm and a molar mass M w of 1.0.106 were determined by means of static and dynamic light scattering. Differential calorimetry (DSC) demonstrated the quantitative incorporation of I into the silicone network.
- a mixture of 100.0 g (0.) was added to an initial charge of 2000 g of water, 12 g of Dodigen R 226 (50% in water) and 10 g of sodium hydroxide solution (10% in water) over a period of 6 hours at 20 ° C , 67 mol) of dimethyldiethoxysilane, 97.4 g (0.72 mol) of methyltrimethoxysilane, 2.6 g (4.1 mmol) of II from Example 2 and 20 g of methanol were added dropwise with stirring. After stirring for a further 2 hours at 20 ° C., a stable, opalescent dispersion with a solids content of 5.3% was obtained.
- a mixture of 160.0 g (1. In 1) was added in the course of 6 hours at 20 ° C. to an initial charge of 2000 g of water, 12 g of Dodigen R 226 (50% in water) and 10 g of sodium hydroxide solution (10% in water) , 08 mol) dimethyldiethoxysilane, 36.7 g (0.27 mol) methyltrimethoxysilane, 2.6 g (4.1 mmol) II from Example 2 and 20 g methanol were added dropwise with stirring. After stirring for a further 2 hours at 20 ° C., a stable, finely divided, white dispersion with 5.4% solids.
- Example 7 The procedure was as in Example 7 with the change that instead of a mixture of 160.0 g of dimethyldiethoxysilane, 36.7 g of methyltrimethoxysilane, 2.6 g of II from Example 2 and 20 g of methanol, a mixture of 160.0 g (1, 08 mol) of dimethyldiethoxysilane, 37.9 g (0.28 mol) of methyltrimethoxysilane and 2.02 g (8.1 mmol) of methacryloxypropyltrimethoxysilane was added dropwise. A stable, finely divided, white dispersion with a solids content of 5.2% was obtained.
- Example 7 The procedure was as in Example 7 with the change that instead of a mixture of 160.0 g of dimethyldiethoxysilane, 36.7 g of methyltrimethoxysilane, 2.6 g of II from Example 2 and 20 g of methanol, a mixture of 160.0 g (1, 08 mol) of dimethyldiethoxysilane and 40.8 g (0.30 mol) of methyltrimethoxysilane was added dropwise. A stable, finely divided, white dispersion with a solids content of 5.1% was obtained.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 16 nm and a molar mass M w of 3.4.106 were determined by means of static and dynamic light scattering. From the light scattering data from Examples 3 and 8, it was possible to determine that the polymethyl methacrylate in the graft copolymer had a hollow spherical structure and the graft copolymer thus had a (silicone) core (polymethyl methacrylate) shell structure.
- the graft copolymer obtained according to Example 8 had a star polymer structure with a crosslinked silicone core in a non-aqueous medium of which had linearly outgoing polymethyl methacrylate graft branches.
- Example 8 The procedure was as in Example 8, with the change that the dispersion from Example 4 was used instead of the dispersion from Example 3.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 16 nm and a molar mass M w of 4.0.106 were determined by means of static and dynamic light scattering.
- the polymethyl methacrylate in the graft copolymer had a hollow spherical structure, and thus the graft copolymer (Silicon) core (polymethyl methacrylate) shell structure.
- the graft copolymer obtained according to Example 9 had a star polymer structure with a crosslinked silicone core in a non-aqueous medium of which had linearly outgoing polymethyl methacrylate graft branches.
- Example 8 The procedure is as in Example 8, with the change that the dispersion from Example 5 is used instead of the dispersion from Example 3.
- An opalescent dispersion with a solids content of 8.1% and a proportion of polymethyl methacrylate in the graft copolymer of 50% is obtained.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 18 nm and a molar mass M w of 5.1.10 Mol were determined by means of static and dynamic light scattering.
- the polymethyl methacrylate in the graft copolymer had a hollow spherical structure, and the graft copolymer thus had a (silicone) core (polymethyl methacrylate) shell structure.
- the graft copolymer obtained according to Example 10 had a star polymer structure with a crosslinked silicone core in a non-aqueous medium of which had linearly outgoing polymethyl methacrylate graft branches.
- Example 8 The procedure was as in Example 8, with the change that the dispersion from Example 4 was used instead of the dispersion from Example 3 and 4.5 g of styrene was added instead of 4.5 g of methyl methacrylate.
- a hydrodynamic radius R h of the monodisperse, spherical particles of 16 nm and a molar mass M w of 3.2.106 was determined by means of static and dynamic light scattering.
- the graft copolymer obtained according to Example 11 had a star polymer structure with a crosslinked silicone core in a non-aqueous medium of which had linearly outgoing polystyrene graft branches.
- Example 7 580 g of dispersion from Example 7 were introduced and 90 g of water / alcohol mixture were distilled off at 30 ° C. in a water jet vacuum. 490 g of the resulting dispersion with a solids content of 5.1% were adjusted to a solids content of 5.0% with 10 g of water. The procedure was then as in Example 12, with the change that 12.5 g of styrene were added instead of 25 g of methyl methacrylate. A finely divided, white, stable dispersion with a solids content of 8.8% and a proportion of polystyrene in the graft copolymer of 33% was obtained.
- Example 12 The procedure was then as in Example 12 with the change that 25 g of styrene, 1 g of potassium peroxodisulfate solution (5% strength in water) and 1 g of sodium bisulfite solution (10% strength in water) were added instead of 25 g of methyl methacrylate and instead of of 80 ° C, a polymerization temperature of 65 ° C was chosen. A finely divided, white, stable dispersion with a solids content of 8.0% and a proportion of polystyrene in the graft copolymer of 33% was obtained.
- Example 12 The procedure was then as in Example 12 with the change that 25 g of styrene, 1 g of potassium peroxodisulfate solution (5% strength in water) and 1 g of sodium bisulfite solution (10% strength in water) were added instead of 25 g of methyl methacrylate and instead of a polymerization temperature of 65 ° C was selected from 80 ° C. A finely divided, white, stable dispersion with a solids content of 8.1% and a proportion of polystyrene in the graft copolymer of 33% was obtained.
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Claims (7)
- Organopolysiloxane réticulé, contenant des groupements formant des radicaux, constitué de
0,2 à 50,0% en poids d'unités de formule générale
[RaSi(O(3-a)/2)-R¹-X-(R¹-Si(O(3-a)/2))bRa] (1),
0 à 80,0% en poids d'unités de formule générale
[R₃SiO1/2] (2),
0 à 99,5% en poids d'unités de formule générale
[R₂SiO2/2] (3),
0 à 99,8% en poids d'unités de formule générale
[RSiO3/2] (4),
et
0 à 80,0% en poids d'unités de formule générale
[SiO4/2] (5),
oùR représente des radicaux hydrocarbures monovalents, identiques ou différents, à liaison SiC, facultativement substitués, en C₁ à C₁₈,R¹ représente des radicaux hydrocarbures bivalents, identiques ou différents, à liaison SiC, facultativement substitués, en C₁ à C₁₈, qui peuvent être interrompus par des radicaux à deux liaisons, liés à chaque extrémité à un atome de carbone, choisis parmi le groupe -O-, -COO-, -OOC-, -CONR-, -NRCO- et -CO-,R représente un atome d'hydrogène ou un radical R,X représente un radical choisi parmi le groupe -N=N-, -O-O-, -S-S- et -C(C₆H₅)₂-C(C₆H₅)₂-,a représente la valeur 0, 1 ou 2 et,b représente la valeur 0 ou 1,
avec la condition que la somme des unités de formules générales (4) et (5) atteigne au moins 0,5% en poids et que au plus 5% en poids de l'organopolysiloxane soient extractibles par le toluène. - Organopolysiloxane suivant la revendication 1, qui possède 0,2 à 50,0% en poids d'unités de formule générale (8)
[(CH₃)aSi(O(3-a)/2)-(CH₂)₃-N(R³)-C(O)-(CH₂)₂-C(CN)(CH₃)-N=]₂
dans laquelleR³ représente un atome d'hydrogène, un radical méthyle ou cyclohexyle, eta présente les significations précédentes. - Procédé de préparation d'organopolysiloxane réticulé, contenant des groupements formant des radicaux suivant la revendication 1 ou 2, dans lequel le silane de formule générale (9)
RaSi((OR⁴)3-a) -R¹-X-(R¹-Si((OR⁴)3-a))bRa (9),
et le composé organosilicié de formule générale (10)
RcSi(OR⁴)4-c (10),
et facultativement, un composé organosilicié d'unités de formule générale (11)
Rd(R⁴O)eSiO4-d-e/2 (11),
oùR⁴ a la signification de R,c a la valeur 0, 1, 2 ou 3,d et e ont, chacun indépendamment l'un de l'autre, la valeur 0, 1, 2, 3 ou 4 et
R, R⁴, X, a et b ont les significations précédentes, sont ajoutés à un mélange agité d'émulsionnant et d'eau. - Procédé de préparation de copolymères greffés, dans lequel95 à 5% en poids d'un organopolysiloxane suivant la revendication 1 ou 2 ou d'un organopolysiloxane prépare suivant la revendication 3,sont mis à réagir en dispersion aqueuse avec 5 à 95% en poids d'un monomère éthyléniquement insaturé.
- Procédé suivant la revendication 4, dans lequel on prépare une dispersion de l'organopolysiloxane et on ajoute le monomère.
- Procédé suivant la revendication 4 ou 5, dans lequel du styrène ainsi que des esters de l'acide acrylique et des esters de l'acide méthacrylique d'alcools aliphatiques avec 1 à 4 atomes de carbone sont introduits comme monomères.
- Copolymère greffé pouvant être obtenu par le procédé suivant l'une quelconque des revendications 4 à 6.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4338421A DE4338421A1 (de) | 1993-11-10 | 1993-11-10 | Pfropfcopolymerisate aus Organopolysiloxanen als Radikalmakroinitiatoren |
DE4338421 | 1993-11-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0659838A1 EP0659838A1 (fr) | 1995-06-28 |
EP0659838B1 true EP0659838B1 (fr) | 1996-04-03 |
Family
ID=6502287
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94117748A Expired - Lifetime EP0659838B1 (fr) | 1993-11-10 | 1994-11-10 | Copolymeres d'organopolysiloxane comme macro-initiateur radicalaire |
Country Status (8)
Country | Link |
---|---|
US (1) | US5523365A (fr) |
EP (1) | EP0659838B1 (fr) |
JP (1) | JP2693391B2 (fr) |
KR (1) | KR0152310B1 (fr) |
AT (1) | ATE136322T1 (fr) |
CA (1) | CA2118173C (fr) |
DE (2) | DE4338421A1 (fr) |
ES (1) | ES2085817T3 (fr) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2721206A1 (fr) | 1994-06-17 | 1995-12-22 | Oreal | Composition capillaire comprenant une dispersion aqueuse de polymères. |
DE69619759T2 (de) * | 1995-10-05 | 2002-11-21 | Mandom Corp | Basismaterial für die Haarkosmetik |
US6136296A (en) * | 1997-04-25 | 2000-10-24 | The Procter & Gamble Company | Personal care compositions |
US6113883A (en) * | 1997-04-25 | 2000-09-05 | The Procter & Gamble Company | Hair styling compositions comprising silicone-containing copolymers |
US6074628A (en) * | 1997-04-25 | 2000-06-13 | Procter & Gamble | Hairspray compositions containing silicon block copolymers |
US5997886A (en) * | 1997-11-05 | 1999-12-07 | The Procter & Gamble Company | Personal care compositions |
US5985294A (en) * | 1997-11-05 | 1999-11-16 | The Procter & Gamble Company | Personal care compositions |
US5968495A (en) * | 1997-11-05 | 1999-10-19 | The Procter & Gamble Company | Personal care compositions |
US5985295A (en) * | 1997-11-05 | 1999-11-16 | The Procter & Gamble Company | Personal care compositions |
US5965115A (en) * | 1997-11-05 | 1999-10-12 | The Procter & Gamble Company | Personal care compositions |
US6093410A (en) * | 1997-11-05 | 2000-07-25 | The Procter & Gamble Company | Personal care compositions |
JP3876946B2 (ja) * | 1998-01-20 | 2007-02-07 | 信越化学工業株式会社 | 帯電付与部材用コーティング剤及びそれを用いた電子写真用キャリア |
US6149898A (en) * | 1998-06-22 | 2000-11-21 | The Procter & Gamble Company | Hair styling compositions containing silicone microemulsions and cationic non-polymeric liquids |
DE19958042A1 (de) * | 1999-12-03 | 2001-06-21 | Invitek Gmbh | Oberflächenmodifizierte Trägermaterialien zur Bindung biologischer Materialien, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP2001192454A (ja) * | 2000-01-14 | 2001-07-17 | Shin Etsu Chem Co Ltd | オルガノポリシロキサン、ゴム用配合剤及びそれを用いたゴム組成物並びにタイヤ |
DE10232993A1 (de) * | 2002-07-19 | 2004-02-05 | Wacker Polymer Systems Gmbh & Co. Kg | Silicon-haltige Polymerisate von ehtylenisch ungesättigten Monomeren |
US7585922B2 (en) * | 2005-02-15 | 2009-09-08 | L'oreal, S.A. | Polymer particle dispersion, cosmetic compositions comprising it and cosmetic process using it |
US8277788B2 (en) * | 2005-08-03 | 2012-10-02 | Conopco, Inc. | Quick dispersing hair conditioning composition |
US7862886B2 (en) * | 2005-08-12 | 2011-01-04 | Fujifilm Corporation | Optical film, antireflection film, processes for producing the same, and polarizing plate and display employing the same |
WO2009033070A1 (fr) * | 2007-09-07 | 2009-03-12 | The Curators Of The University Of Missouri | Matériaux composites réticulés de polymère monolithiques et procédés de préparation |
WO2009032568A1 (fr) * | 2007-09-07 | 2009-03-12 | The Curators Of The University Of Missouri | Ensembles préformés de nanoparticules d'origine sol-gel en tant qu'échafaudages en 3d pour des composites et des aérogels |
EP2571912A1 (fr) | 2010-05-19 | 2013-03-27 | Evonik Goldschmidt GmbH | Copolymères séquencés de polysiloxane et leur utilisation dans des formulations cosmétiques |
JP2013527286A (ja) | 2010-05-19 | 2013-06-27 | エヴォニク ゴールドシュミット ゲーエムベーハー | ポリシロキサンブロックコポリマーおよび化粧料配合物におけるその使用 |
KR102093964B1 (ko) * | 2016-08-09 | 2020-03-26 | 주식회사 엘지화학 | 아크릴계 가공조제 및 이를 포함하는 염화비닐계 수지 조성물 |
KR102247351B1 (ko) * | 2017-12-18 | 2021-04-30 | 주식회사 엘지화학 | 코어-쉘 공중합체 제조방법, 코어-쉘 공중합체 및 이를 포함하는 수지 조성물 |
JP2021008372A (ja) | 2019-06-28 | 2021-01-28 | 三菱鉛筆株式会社 | ガラス状炭素成形体 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3719650A (en) * | 1970-10-21 | 1973-03-06 | Union Carbide Corp | Hydrolyzable functional sylyl alkyl alkyl peroxides |
US3775386A (en) * | 1971-05-25 | 1973-11-27 | Du Pont | Polymers having silicon containing end groups and a process for their preparation |
DE3226091C2 (de) * | 1982-07-13 | 1986-11-20 | Degussa Ag, 6000 Frankfurt | Polymere Di-, Tri- oder Tetrasulfide, Verfahren zu ihrer Herstellung und Verwendung |
JPH0233053B2 (ja) * | 1985-04-30 | 1990-07-25 | Osaka City | Azokiganjuhorishirokisanamido |
JPS6317291A (ja) * | 1986-07-09 | 1988-01-25 | Seiji Kumakawa | 結晶成長方法及びその装置 |
JPH0647620B2 (ja) * | 1987-02-02 | 1994-06-22 | 東レ・ダウコーニング・シリコーン株式会社 | ジオルガノポリシロキサン・アゾベンゼン交互共重合体およびその製造方法 |
JPH0397735A (ja) * | 1989-08-14 | 1991-04-23 | Minnesota Mining & Mfg Co <3M> | シロキサンイニファーター化合物 |
FR2652582B1 (fr) * | 1989-10-02 | 1992-01-24 | Rhone Poulenc Chimie | Disulfure de thiurame greffe polydiorganosiloxane et son utilisation lors de la polymerisation radicalaire de monomeres vinyliques. |
DE4040986A1 (de) * | 1990-12-20 | 1992-06-25 | Wacker Chemie Gmbh | Elastomere pfropfcopolymerisate mit kern-huelle-struktur |
JP3126772B2 (ja) * | 1991-10-29 | 2001-01-22 | ジェイエスアール株式会社 | 熱可塑性樹脂の製造方法 |
JP3271376B2 (ja) * | 1992-06-09 | 2002-04-02 | 和光純薬工業株式会社 | アゾ基含有ポリシロキサンアミドの製造法 |
JPH069716A (ja) * | 1992-06-26 | 1994-01-18 | C I Kasei Co Ltd | アゾ基含有ポリシロキサンエステル系重合開始剤 |
DE4225978C1 (de) * | 1992-08-06 | 1994-04-07 | Degussa | Geformte Organosiloxan-Polykondensate, Verfahren zu ihrer Herstellung und Verwendung |
-
1993
- 1993-11-10 DE DE4338421A patent/DE4338421A1/de not_active Withdrawn
-
1994
- 1994-10-11 US US08/320,369 patent/US5523365A/en not_active Expired - Fee Related
- 1994-10-14 CA CA002118173A patent/CA2118173C/fr not_active Expired - Fee Related
- 1994-11-04 KR KR1019940028885A patent/KR0152310B1/ko not_active IP Right Cessation
- 1994-11-08 JP JP6273767A patent/JP2693391B2/ja not_active Expired - Lifetime
- 1994-11-10 AT AT94117748T patent/ATE136322T1/de not_active IP Right Cessation
- 1994-11-10 EP EP94117748A patent/EP0659838B1/fr not_active Expired - Lifetime
- 1994-11-10 ES ES94117748T patent/ES2085817T3/es not_active Expired - Lifetime
- 1994-11-10 DE DE59400185T patent/DE59400185D1/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE59400185D1 (de) | 1996-05-09 |
ES2085817T3 (es) | 1996-06-01 |
US5523365A (en) | 1996-06-04 |
JPH07188414A (ja) | 1995-07-25 |
EP0659838A1 (fr) | 1995-06-28 |
KR950014185A (ko) | 1995-06-15 |
KR0152310B1 (ko) | 1998-10-15 |
CA2118173A1 (fr) | 1995-05-11 |
CA2118173C (fr) | 1998-04-07 |
DE4338421A1 (de) | 1995-05-11 |
JP2693391B2 (ja) | 1997-12-24 |
ATE136322T1 (de) | 1996-04-15 |
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